Energetics of chloride adlayers on Au(100) electrodes: Grand-canonical Monte Carlo simulations and ab-intio thermodynamics

Based on extensive DFT calculations for 84 different geometrical configurations of adlayers, we have investigated the adsorption of chlorine atoms on the unreconstructed Au(100) surface for different coverages. We have confirmed the stability of several structures observed in experiments. In particular, the stability of defective c(2 × 2) arrangements showing patches separated by domain boundaries has been established. We have developed a strategy to use DFT parameters in grand canonical Monte Carlo simulations. Both the simulations and ab-initio thermodynamics show structural changes with the electrochemical potential consistent with experiments. [Display omitted]